ELECTRON TRANSFER MAKES D3h (78:5) CAGE EASY TO FORM M2@C78(M = La, Ce): A RELATIVISTIC DENSITY-FUNCTIONAL THEORY STUDY

Abstract

Applying relativistic density functional theory to isomers of C 78 and M 2@ C 78( M = La , Ce ), we calculate and analyze the relative energies and HOMO–LUMO gaps of neutral and hexaanion ( -6 charged) C 78 isomers. Our results indicate that the [Formula: see text] (5) isomer is the most stable, and it illustrate that electron transfer plays an important role in controlling the stability of endohedral metallofullerenes. We also calculate the electronic structures of there neutral isomers, and based on their LUMO + 2 and LUMO + 3 gaps, we explain why it is easier to encage two metal atoms in D3h′ (78:5). To further elucidate this issue, we theoretically characterize M 2@ C 78( M = La , Ce ) and compare the relative energies and the HOMO–LUMO gap of the two isomers M 2@ C 78 (4) and the M 2@ C 78 (5) ( M = La , Ce ). The results indicate that M 2@ C 78 (5) is more stable than M 2@ C 78 (4). Furthermore, the good agreement between the experimental and computed 13C NMR chemical shift of the isomer M 2@ C 78 (5) provided strong evidence that M 2@ C 78 forms a D3h′ (78:5) cage.